US9403926B2 - Process for producing copolymers of propylene - Google Patents
Process for producing copolymers of propylene Download PDFInfo
- Publication number
- US9403926B2 US9403926B2 US14/758,117 US201314758117A US9403926B2 US 9403926 B2 US9403926 B2 US 9403926B2 US 201314758117 A US201314758117 A US 201314758117A US 9403926 B2 US9403926 B2 US 9403926B2
- Authority
- US
- United States
- Prior art keywords
- propylene
- copolymer
- weight
- mixture
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 229920005606 polypropylene copolymer Polymers 0.000 title claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 107
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 77
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000004711 α-olefin Substances 0.000 claims abstract description 67
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000005977 Ethylene Substances 0.000 claims abstract description 59
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 56
- -1 propylene, ethylene Chemical group 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims description 103
- 229920001577 copolymer Polymers 0.000 claims description 95
- 229920000642 polymer Polymers 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 46
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 43
- 239000011541 reaction mixture Substances 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 31
- 238000010926 purge Methods 0.000 claims description 29
- 239000002685 polymerization catalyst Substances 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 61
- 239000003054 catalyst Substances 0.000 description 23
- 238000005243 fluidization Methods 0.000 description 22
- 239000012071 phase Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
Definitions
- the present invention is directed to a process for producing copolymers of propylene. Especially, the present invention is directed to an improved process for producing copolymers of propylene with at least two comonomers. In particular, the present invention is directed to an improved process for producing copolymers of propylene with ethylene and at least one alpha-olefin having from 4 to 10 carbon atoms where the content of unreacted comonomer within the copolymer is low.
- alpha-olefins containing 4 or more carbon atoms as comonomers with propylene is advantageous, as they are in some aspects advantageous to ethylene.
- the problem in such comonomers is that they are often less reactive than propylene and ethylene. Further, they are also less volatile.
- the polymer when the polymer is withdrawn from the polymerization process it often contains significant amount of unreacted alpha-olefin which may cause deterioration in organoleptic properties, such as offensive taste or odour or both.
- the removal of such residual hydrocarbon from the polymer requires additional purging stages or at least more intensive purging. During such process stages there is also an increased risk for forming explosive gas mixtures which is a process safety issue.
- the present invention aims to provide a process for copolymerizing propylene with ethylene and at least one alpha-olefin comonomer having from 4 to 10 carbon atoms where the amount of unreacted comonomer in the polymer is reduced but where the polymer still has the advantageous properties characteristic for copolymers of propylene with alpha-olefins containing from 4 to 10 carbon atoms.
- WO-A-2009019169 discloses a process where terpolymers of ethylene, propylene and 1-butene were produced in two interconnected gas phase polymerization zones. The process was reported to produce copolymers having a fixed ratio between ethylene and 1-butene units and a higher melting temperature for a given comonomer content compared to the copolymers produced by using prior art processes.
- WO-A-2009130092 discloses that terpolymers of ethylene, propylene and 1-butene were produced in slurry in liquid propylene.
- WO-A-2008074699 discloses that terpolymers of ethylene, propylene and 1-butene were produced in cascaded reactor system of two loop reactors and a gas phase reactor by gradually reducing the concentrations of ethylene and 1-butene in the feed to the loop reactors.
- the present invention provides a process of copolymerizing propylene, ethylene and at least one alpha-olefin having from 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst in three cascaded polymerization stages comprising the steps of:
- propylene is polymerized in at least three stages.
- ethylene and an alpha-olefin having from 4 to 10 carbon atoms are introduced into the polymerization reactors as fresh monomer feeds.
- propylene optionally together with ethylene, is introduced as a fresh monomer feed.
- additional monomer mixture is meant a fresh monomer feed into a polymerization stage.
- the first additional monomer mixture denotes the fresh monomer feed into the second polymerization stage and the second additional monomer mixture denotes the fresh monomer feed into the third polymerization stage.
- fresh monomer monomer which has been introduced directly into a reactor so that the monomer has not passed via another reactor.
- Residual monomer means monomer which is carried over from a previous polymerization stage.
- the process conditions are adjusted such that the final polymer composition obtained by the process contains from 3 to 10% by weight by weight of units derived from alpha-olefin containing 4 to 10 carbon atoms, from 1 to 5% by weight of ethylene units and from 85 to 96% by weight of propylene units.
- the alpha-olefin having from 4 to 10 carbon atoms is 1-butene, 1-hexene or 1-octene.
- the alpha-olefin having from 4 to 10 carbon atoms is 1-butene.
- the final polymer composition preferably has a melt index MFR 2 of from 0.1 to 15 g/10 min, more preferably from 0.5 to 10 g/10 min. A more detailed description of the polymerization conditions is given below.
- the polymerisation can be carried out in the presence of a metallocene catalyst or Ziegler-Natta-type catalyst, the latter is in particular preferred.
- a Ziegler-Natta type catalyst typically used in the present invention for propylene polymerization is stereospecific, high yield Ziegler-Natta catalyst comprising as essential components Mg, Ti, Al and Cl.
- This type of catalysts comprise typically in addition to a solid transition metal (like Ti) component a cocatalyst(s) as well external donor(s) as stereoregulating agent.
- These compounds may be supported on a particulate support, such as inorganic oxide, like silica or alumina, or, usually, the magnesium halide may form the solid support. It is also possible that solid catalysts are self supported, i.e. the catalysts are not supported on an external support, but are prepared via emulsion-solidification method.
- the solid transition metal component usually also comprises an electron donor (internal electron donor).
- Suitable internal electron donors are, among others, esters of carboxylic acids, like phthalates, citraconates, and succinates. Also oxygen- or nitrogen-containing silicon compounds may be used.
- the cocatalyst used in combination with the transition metal compound typically comprises an aluminium alkyl compound.
- the aluminium alkyl compound is preferably trialkyl aluminium such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium or tri-n-octylaluminium. However, it may also be an alkylaluminium halide, such as diethylaluminium chloride, dimethylaluminium chloride and ethylaluminium sesquichloride. Triethylaluminium is an especially preferred aluminium alkyl compound.
- the aluminium alkyl is preferably introduced to reach a desired ratio of the aluminium to titanium. Suitable ratios depend on the catalyst and lie within the range of from 30 to 1000 mol/mol, such as 50 to 600 mol/mol.
- the catalyst also comprises an external electron donor.
- Suitable electron donors known in the art include ethers, ketones, amines, alcohols, phenols, phosphines and silanes.
- Silane type external donors are typically organosilane compounds containing Si—OCOR, Si—OR, or Si—NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl with 1-20 carbon atoms are known in the art.
- Organosilane compounds are preferred external donors, with dicyclopentyldimethoxysilane and cyclohexylmethyldimethoxysilane being especially preferred.
- the organosilane compound is typically introduced to keep a desired ratio aluminium alkyl and the silane compound, such as from 3 to 20, or from 4 to 10.
- Suitable catalysts and compounds in catalysts are shown in among others, in WO-A-87/07620, WO-A-92/21705, WO-A-93/11165, WO-A-93/11166, WO-A-93/19100, WO-A-97/36939, WO-A-98/12234, WO-A-99/33842, WO-A-03/000756, WO-A-03/000757, WO-A-03/000754, WO-A-03/000755, WO-A-2004/029112, WO-A-92/19659, WO-A-92/19653, WO-A-92/19658, U.S. Pat. No.
- the prepolymerization is conducted in a continuous manner as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with minor amount of other reactants and optionally inert components dissolved therein.
- the prepolymerization is conducted in a continuous stirred tank reactor or a loop reactor.
- the prepolymerization reaction is typically conducted at a temperature of 0 to 60° C., preferably from 10 to 50° C.
- the pressure in the prepolymerization reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase.
- the pressure may be from 20 to 100 bar, for example 30 to 70 bar.
- reaction conditions are well known in the art as disclosed, among others, in GB-A-1580635.
- comonomers are ethylene or alpha-olefins having from 4 to 10 carbon atoms.
- suitable comonomers are ethylene, 1-butene, 1-hexene, 1-octene or their mixtures.
- a first copolymer of propylene, ethylene and at least one alpha-olefin containing 4 to 10 carbon atoms is produced. This is done by introducing a polymerization catalyst, optionally through the prepolymerization stage as disclosed above, into the first polymerization stage together with a first monomer mixture containing propylene, ethylene and at least one alpha-olefin containing 4 to 10 carbon atoms. The contents of the different monomers are controlled to obtain the desired contents of the monomeric constituents in the first copolymer.
- the first copolymer contains from 5 to 15% by weight of units derived from alpha-olefin(s) containing 4 to 10 carbon atoms, from 0.1 to 3% by weight of ethylene units and from 82 to 94.9% by weight of propylene units.
- the first copolymer contains from 6 to 12% by weight of units derived from alpha-olefin(s) containing 4 to 10 carbon atoms, from 0.5 to 2% by weight of ethylene units and from 86 to 93.5% by weight of propylene units.
- the first copolymer is a semicrystalline copolymer of propylene and thus not amorphous. It preferably has a fraction of xylene soluble material of from 2 to 10%, more preferably from 2 to 5% by weight.
- the polymerization in the first polymerization zone is preferably conducted in slurry. Then the polymer particles formed in the polymerization, together with the catalyst fragmented and dispersed within the particles, are suspended in the fluid hydrocarbon. The slurry is agitated to enable the transfer of reactants from the fluid into the particles.
- Slurry polymerization is preferably a so called bulk polymerization.
- bulk polymerization is meant a process where the polymerization is conducted in a liquid monomer essentially in the absence of an inert diluent.
- the monomers used in commercial production are never pure but always contain aliphatic hydrocarbons as impurities.
- the propylene monomer may contain up to 5% of propane as an impurity.
- propane As propylene is consumed in the reaction and also recycled from the reaction effluent back to the polymerization, the inert components tend to accumulate, and thus the reaction medium may comprise up to 40 wt-% of other compounds than monomer. It is to be understood, however, that such a polymerization process is still within the meaning of “bulk polymerization”, as defined above.
- the temperature in the slurry polymerization is typically from 50 to 110° C., preferably from 60 to 100° C. and in particular from 65 to 95° C.
- the pressure is from 1 to 150 bar, preferably from 10 to 100 bar.
- the slurry polymerization may be conducted in any known reactor used for slurry polymerization.
- reactors include a continuous stirred tank reactor and a loop reactor. It is especially preferred to conduct the polymerization in loop reactor.
- the slurry is circulated with a high velocity along a closed pipe by using a circulation pump.
- Loop reactors are generally known in the art and examples are given, for instance, in U.S. Pat. No. 4,582,816, U.S. Pat. No. 3,405,109, U.S. Pat. No. 3,324,093, EP-A-479186 and U.S. Pat. No. 5,391,654.
- the slurry may be withdrawn from the reactor either continuously or intermittently.
- a preferred way of intermittent withdrawal is the use of settling legs where the solids concentration of the slurry is allowed to increase before withdrawing a batch of the concentrated slurry from the reactor.
- the use of settling legs is disclosed, among others, in U.S. Pat. No. 3,374,211, U.S. Pat. No. 3,242,150 and EP-A-1310295.
- Continuous withdrawal is disclosed, among others, in EP-A-891990, EP-A-1415999, EP-A-1591460 and EP-A-1860125.
- the continuous withdrawal may be combined with a suitable concentration method, as disclosed in EP-A-1860125 and EP-A-1591460.
- the first polymerization stage is conducted as slurry polymerization in a loop reactor it has been found that if the first monomer mixture contains from 0.05 to 2.0% by weight of ethylene, from 5 to 40% by weight of alpha-olefin(s) containing 4 to 10 carbon atoms and from 95 to 58% by weight of propylene good results are obtained.
- the first monomer mixture contains from 0.05 to 2.0% by weight of ethylene, from 5 to 40% by weight of alpha-olefin(s) containing 4 to 10 carbon atoms and from 95 to 58% by weight of propylene good results are obtained.
- different monomer mixture compositions may be required.
- a first copolymer mixture comprising the first copolymer and a second copolymer is formed. This is done by introducing the particles of the first copolymer, containing active catalyst dispersed therein, and a second monomer mixture into the second polymerization stage. This causes the second copolymer to form on the particles containing the first copolymer.
- the first additional monomer mixture preferably contains propylene, ethylene and at least one alpha-olefin containing 4 to 10 carbon atoms. Also in the second polymerization stage the contents of the different monomers are controlled to obtain the desired contents of the monomeric constituents in the first copolymer mixture.
- the first copolymer mixture contains from 4 to 12% by weight by weight of units derived from alpha-olefin containing 4 to 10 carbon atoms, from 0.5 to 5% by weight of ethylene units and from 83 to 95.5% by weight of propylene units.
- the first copolymer mixture contains from 5 to 8% by weight of units derived from alpha-olefin(s) containing 4 to 10 carbon atoms, from 0.5 to 2% by weight of ethylene units and from 90 to 94.5% by weight of propylene units.
- the first copolymer mixture preferably comprises from 40 to 60% by weight of the first copolymer and from 60 to 40% by weight of the second copolymer.
- the second copolymer of propylene is a semicrystalline copolymer and thus not amorphous.
- Second copolymer preferably has a fraction of polymer soluble in xylene of from 2 to 10%, more preferably from 4 to 8% by weight.
- the first additional monomer mixture it is not necessary for the first additional monomer mixture to contain the alpha-olefin containing 4 to 10 carbon atoms. This can be the case, for instance, when the reaction mixture carried over from the first polymerization stage contains a sufficient amount of the alpha-olefin to reach the desired product properties. This can be the case when the first polymerization stage was conducted in slurry and the slurry is directly transferred to the second polymerization stage without removing the reaction mixture from the polymer. However, there are many instances where the first additional monomer mixture needs to contain the alpha-olefin containing from 4 to 10 carbon atoms.
- the composition of the first additional monomer mixture is adjusted so that the fluidization gas has a ratio of ethylene to propylene of about 5 to 50 mol/kmol (or, mol/1000 mol), a ratio of the alpha-olefin to propylene of about 100 to 300 mol/kmol and contains from 50 to 95 mol-% propylene.
- the second polymerization stage is preferably conducted in gas phase by polymerizing the monomers in a fluidized bed.
- a fluidized bed gas phase reactor an olefin is polymerized in the presence of a polymerization catalyst in an upwards moving gas stream.
- the reactor typically contains a fluidized bed comprising the growing polymer particles containing the active catalyst, said fluidized bed having its base above a fluidization grid.
- the polymer bed is fluidized with the help of the fluidization gas comprising the olefin monomer, eventual comonomer(s), eventual chain growth controllers or chain transfer agents, such as hydrogen, and eventual inert gas.
- the fluidization gas is introduced into an inlet chamber at the bottom of the reactor.
- the inlet pipe may be equipped with a flow dividing element as known in the art, e.g. U.S. Pat. No. 4,933,149 and EP-A-684871.
- One or more of the above-mentioned components may be continuously added into the fluidization gas to compensate for losses caused, among other, by reaction or product withdrawal.
- the gas flow is passed upwards through a fluidization grid into the fluidized bed.
- the purpose of the fluidization grid is to divide the gas flow evenly through the cross-sectional area of the bed.
- the fluidization grid may be arranged to establish a gas stream to sweep along the reactor walls, as disclosed in WO-A-2005/087361.
- Other types of fluidization grids are disclosed, among others, in U.S. Pat. No. 4,578,879, EP-A-600414 and EP-A-721798. An overview is given in Geldart and Bayens: The Design of Distributors for Gas-fluidized Beds, Powder Technology, Vol. 42, 1985.
- the fluidization gas passes through the fluidized bed.
- the superficial velocity of the fluidization gas must be higher that minimum fluidization velocity of the particles contained in the fluidized bed, as otherwise no fluidization would occur.
- the velocity of the gas should be lower than the onset velocity of pneumatic transport, as otherwise the whole bed would be entrained with the fluidization gas.
- the minimum fluidization velocity and the onset velocity of pneumatic transport can be calculated when the particle characteristics are known by using common engineering practise. An overview is given, among others in Geldart: Gas Fluidization Technology, J. Wiley & Sons, 1986.
- the reactive components of the gas such as monomers and chain transfer agents, react in the presence of the catalyst to produce the polymer product.
- the gas is heated by the reaction heat.
- the unreacted fluidization gas is removed from the top of the reactor and cooled in a heat exchanger to remove the heat of reaction.
- the gas is cooled to a temperature which is lower than that of the bed to prevent the bed from heating because of the reaction. It is possible to cool the gas to a temperature where a part of it condenses.
- the liquid droplets enter the reaction zone they are vaporised.
- the vaporisation heat then contributes to the removal of the reaction heat.
- This kind of operation is called condensed mode and variations of it are disclosed, among others, in WO-A-2007/025640, U.S. Pat. No. 4,543,399, EP-A-699213 and WO-A-94/25495.
- condensing agents are non-polymerizable components, such as n-pentane, isopentane, n-butane or isobutane, which are at least partially condensed in the cooler.
- the gas is then compressed and recycled into the inlet chamber of the reactor.
- fresh reactants Prior to the entry into the reactor fresh reactants are introduced into the fluidization gas stream to compensate for the losses caused by the reaction and product withdrawal. It is generally known to analyze the composition of the fluidization gas and introduce the gas components to keep the composition constant. The actual composition is determined by the desired properties of the product and the catalyst used in the polymerization.
- the polymeric product may be withdrawn from the gas phase reactor either continuously or intermittently. Combinations of these methods may also be used. Continuous withdrawal is disclosed, among others, in WO-A-00/29452. Intermittent withdrawal is disclosed, among others, in U.S. Pat. No. 4,621,952, EP-A-188125, EP-A-250169 and EP-A-579426.
- the top part of the gas phase reactor may include a so called disengagement zone.
- the diameter of the reactor is increased to reduce the gas velocity and allow the particles that are carried from the bed with the fluidization gas to settle back to the bed.
- the bed level may be observed by different techniques known in the art. For instance, the pressure difference between the bottom of the reactor and a specific height of the bed may be recorded over the whole length of the reactor and the bed level may be calculated based on the pressure difference values. Such a calculation yields a time-averaged level. It is also possible to use ultrasonic sensors or radioactive sensors. With these methods instantaneous levels may be obtained, which of course may then be averaged over time to obtain a time-averaged bed level.
- antistatic agent(s) may be introduced into the gas phase reactor if needed. Suitable antistatic agents and methods to use them are disclosed, among others, in U.S. Pat. No. 5,026,795, U.S. Pat. No. 4,803,251, U.S. Pat. No. 4,532,311, U.S. Pat. No. 4,855,370 and EP-A-560035. They are usually polar compounds and include, among others, water, ketones, aldehydes and alcohols.
- the reactor may also include a mechanical agitator to further facilitate mixing within the fluidized bed.
- a mechanical agitator to further facilitate mixing within the fluidized bed.
- An example of suitable agitator design is given in EP-A-707513.
- the fluidized bed polymerization reactor is operated at a temperature within the range of from 50 to 100° C., preferably from 65 to 90° C.
- the pressure is suitably from 10 to 40 bar, preferably from 15 to 30 bar.
- a second copolymer mixture comprising the first copolymer mixture and a third polymer is formed. This is done by introducing the mixture of the particles comprising the first copolymer mixture and the second fluid reaction mixture, together with a second additional monomer mixture, into the third polymerization stage. This causes the third polymer to form on the particles containing the first copolymer mixture.
- the third polymerization stage is conducted in a fluidized bed gas phase reactor.
- the monomer is in vapour phase around the polymer particles and accesses the active catalyst contained in the particles.
- heavier comonomers such as the alpha-olefins having from 4 to 10 carbon atoms, are not completely vaporized but are at least partly condensed on the polymer particles where they can easily access the active sites of the catalyst.
- the second additional monomer mixture contains propylene and preferably also ethylene. Also in the third polymerization stage the contents of the monomers are controlled to obtain the desired contents of the monomeric constituents in the second copolymer mixture. As explained above, even though no fresh alpha-olefin having 4 to 10 carbon atoms is introduced into the third polymerization stage, the third copolymer produced therein is still a ternary copolymer of propylene, ethylene and said alpha-olefin.
- the second copolymer mixture contains from 3 to 10% by weight by weight of units derived from alpha-olefin containing 4 to 10 carbon atoms, from 1 to 5% by weight of ethylene units and from 85 to 96% by weight of propylene units.
- the second copolymer mixture contains from 6 to 8% by weight of units derived from alpha-olefin(s) containing 4 to 10 carbon atoms, from 1 to 2% by weight of ethylene units and from 90 to 93% by weight of propylene units.
- the second copolymer mixture preferably contains from 75 to 96% by weight, more preferably from 80 to 95% by weight, of the first copolymer mixture and from 4 to 25% by weight, more preferably from 5 to 20% by weight of the third polymer.
- the third polymer of propylene is a semicrystalline polymer and thus not amorphous.
- the third polymer preferably has a fraction of polymer soluble in xylene of from 2 to 10%, more preferably from 4 to 8% by weight.
- the third polymer is preferably a third copolymer because residual comonomer from the second polymerization stage is carried over to the third polymerization stage together with the polymer. Furthermore, it is preferred to feed additional ethylene together with propylene into the third polymerization stage.
- the second additional monomer mixture consists of from 93 to 99.5% by weight of propylene and from 0.5 to 7% by weight of ethylene.
- the purging step is conducted in a purge vessel where the polymer is contacted with a purge gas.
- the temperature during the purging step is from 30 to 110° C., preferably from 30 to 95° C. and more preferably from 40 to 80° C.
- the average residence time is from 5 to 240 minutes, preferably from 10 to 200 minutes.
- the purging step is conducted continuously.
- the polymer particles are introduced to the top of the purge vessel and removed from the bottom. Thereby a downward flow of polymer particles is established.
- the purge gas is typically introduced at the bottom of the purge vessel so as to achieve a counter-current flow of particles and gas.
- the purge gas preferably contains an inert gas, such as nitrogen, or a gas capable of deactivating the catalyst, such as steam, or a mixture thereof.
- An especially preferred purge gas is nitrogen, optionally containing up to 5% steam.
- the gas flow is selected so that no fluidization of the polymer particles occurs in the purge vessel. Thereby a narrow residence time distribution of the polymer particles is obtained and the process has a good efficiency.
- the polymer particles are mixed with additives and extruded to pellets as it is known in the art.
- Preferably co-rotating twin screw extruder is used for the extrusion step.
- Such extruders are manufactured, for instance, by Coperion (Werner & Pfleiderer) and Japan Steel Works.
- the volatile components as described above were determined by using a gas chromatograph and a headspace method.
- the equipment was a Hewlett Packard gas chromatograph with a 25 m ⁇ 0.32 mm ⁇ 2.5 ⁇ m (length ⁇ diameter ⁇ size of packing material) non-polar column filled with DB-1 (100% dimethyl polysiloxane).
- a flame ionisation detector was used with hydrogen as a fuel gas.
- Helium at 10 psi was used as a carrier gas with a flow rate of 3 ml/min. After the injection of the sample the oven temperature was maintained at 50° C. for 3 minutes, after which it was increased at a rate of 12° C./min until it reached 200° C. Then the oven was maintained at that temperature for 4 minutes, after which the analysis was completed.
- the analysis was conducted as follows: The polymer sample (about 2 grams) was placed in the 20 ml injection flask, which was thermostated to 120° C. and kept at that temperature for one hour. A gas sample from the injection flask was then injected into the GC. Before the analysis, a blind run was conducted, where an injection from an empty flask was made.
- Melt flow rate (MFR, MFR 2 ) was determined according to ISO 1133 at 230° C. under the load of 2.16 kg.
- Ethylene content in propylene polymer was measured by Fourier transmission infrared spectroscopy (FTIR).
- FTIR Fourier transmission infrared spectroscopy
- a thin film of the sample was prepared by hot-pressing.
- the area of —CH2- absorption peak (800-650 cm ⁇ 1 ) was measured with Perkin Elmer FTIR 1600-spectrometer.
- the method was calibrated by ethylene content data measured by 13 C NMR.
- the 1-butene content was measured by using FTIR according to the procedure described above. The butene content was determined from the peak at 767 cm ⁇ 1 . The base line was determined between wave numbers 780 and 750 cm ⁇ 1 .
- the amount of xylene soluble fraction was determined according to ISO 16152.
- a stirred tank reactor having a volume of 45 dm 3 was operated as liquid-filled at a temperature of 27° C. and a pressure of 49 bar.
- propylene so much that the average residence time in the reactor was 0.3 hours together with 1.5 g/h hydrogen and 0.7 g/h of polymerization catalyst prepared according to Catalyst Preparation Example above with triethyl aluminium (TEA) as a cocatalyst and dicyclopentyldimethoxysilane (DCPDMS) as external donor so that the molar ratio of TEA/Ti was about 570 and TEA/DCPDMS was 4.7.
- TEA triethyl aluminium
- DCPDMS dicyclopentyldimethoxysilane
- the slurry from this prepolymerization reactor was directed to a loop reactor having a volume of 150 dm 3 together with 160 kg/h of propylene.
- the loop reactor was operated at a temperature of 70° C. and a pressure of 49 bar.
- Ethylene and 1-butene were introduced at feed rates of 0.4 and 45 kg/h, respectively.
- Hydrogen was introduced so that the ratio of hydrogen to propylene was 5.4 mol/kmol.
- the production rate of propylene copolymer was 30 kg/h, the melt flow rate MFR 2 was 11 g/10 min and the contents of ethylene and 1-butene units in the copolymer were 0.1 and 8% by weight, respectively.
- the polymer slurry from the loop reactor was directly conducted into a first gas phase reactor operated at a temperature of 79° C. and a pressure of 19 bar.
- a first gas phase reactor operated at a temperature of 79° C. and a pressure of 19 bar.
- Into the reactor were fed additional propylene, ethylene, 1-butene and hydrogen, as well as nitrogen as an inert gas, so that the content of propylene was 50% by mole and the ratio of hydrogen to propylene was 41 mol/kmol, ethylene to propylene was 55 mol/kmol and 1-butene to propylene 190 mol/kmol.
- the production rate in the reactor was 15 kg/h and the polymer withdrawn from the reactor had a melt flow rate MFR 2 of 6.4 g/10 min and a content of ethylene and 1-butene units in the copolymer of 2.0 and 8.6% by weight, respectively.
- the reaction mixture from the first gas phase reactor was introduced into a purge bin where a settled bed of copolymer was purged with a purge gas containing nitrogen and steam.
- the average residence time of the polymer in the purge bin was 30 minutes at a temperature of 60° C.
- the polymer withdrawn from the reactor was mixed with effective amounts of Irgafos 168, Irganox 1010 and hydrotalcite.
- the mixture of polymer and additives was then extruded to pellets by using a ZSK70 extruder (product of Coperion) under nitrogen atmosphere.
- a stirred tank reactor having a volume of 45 dm 3 was operated as liquid-filled at a temperature of 28° C. and a pressure of 52 bar.
- propylene so much that the average residence time in the reactor was 0.3 hours together with 2.0 g/h hydrogen and 1.4 g/h of polymerization catalyst prepared according to Catalyst Preparation Example above with triethyl aluminium (TEA) as a cocatalyst and dicyclopentyldimethoxysilane (DCPDMS) as external donor so that the molar ratio of TEA/Ti was about 460 and TEA/DCPDMS was 6.
- TEA triethyl aluminium
- DCPDMS dicyclopentyldimethoxysilane
- the slurry from this prepolymerization reactor was directed to a loop reactor having a volume of 150 dm 3 together with 150 kg/h of propylene.
- the loop reactor was operated at a temperature of 67° C. and a pressure of 51 bar.
- Ethylene and 1-butene were introduced at feed rates of 0.7 and 40 kg/h, respectively.
- Hydrogen was introduced so that the ratio of hydrogen to propylene was 5.7 mol/kmol.
- the production rate of propylene copolymer was 30 kg/h, the melt flow rate MFR 2 was 7 g/10 min and the contents of ethylene and 1-butene units in the copolymer were 0.45 and 9.8% by weight, respectively.
- the polymer slurry from the loop reactor was directly conducted into a first gas phase reactor operated at a temperature of 79° C. and a pressure of 19 bar.
- a first gas phase reactor operated at a temperature of 79° C. and a pressure of 19 bar.
- additional propylene, ethylene, 1-butene and hydrogen, as well as nitrogen as an inert gas so that the content of propylene was 72% by mole and the ratio of hydrogen to propylene was 90 mol/kmol, ethylene to propylene was 19 mol/kmol and 1-butene to propylene 185 mol/kmol.
- the production rate in the reactor was 42 kg/h and the polymer withdrawn from the reactor had a melt flow rate MFR 2 of 6.1 g/10 min and a content of ethylene and 1-butene units in the copolymer of 1.6 and 8.0% by weight, respectively.
- the reaction mixture from the first gas phase reactor was introduced into a purge bin where a settled bed of copolymer was purged with a purge gas containing nitrogen and steam.
- the average residence time of the polymer in the purge bin was 30 minutes at a temperature of 60° C.
- the polymer withdrawn from the reactor was mixed with effective amounts of Irgafos 168, Irganox 1010 and hydrotalcite.
- the mixture of polymer and additives was then extruded to pellets by using a ZSK70 extruder (product of Coperion) under nitrogen atmosphere.
- a stirred tank reactor having a volume of 45 dm 3 was operated as liquid-filled at a temperature of 28° C. and a pressure of 52 bar.
- propylene so much that the average residence time in the reactor was 0.3 hours together with 2.0 g/h hydrogen and 1.3 g/h of polymerization catalyst prepared according to Catalyst Preparation Example above with triethyl aluminium (TEA) as a cocatalyst and dicyclopentyldimethoxysilane (DCPDMS) as external donor so that the molar ratio of TEA/Ti was about 470 and TEA/DCPDMS was 6.
- TEA triethyl aluminium
- DCPDMS dicyclopentyldimethoxysilane
- the slurry from this prepolymerization reactor was directed to a loop reactor having a volume of 150 dm 3 together with 150 kg/h of propylene.
- the loop reactor was operated at a temperature of 67° C. and a pressure of 51 bar.
- the ratio of hydrogen to propylene was 5.8 mol/kmol.
- Into the reactor were introduced 0.9 kg/h of ethylene and 40 kg/h 1-butene.
- the production rate of propylene copolymer was 32 kg/h, the melt flow rate MFR 2 was 7.4 g/10 min and the contents of ethylene and 1-butene units in the copolymer were 1.1 and 9.0% by weight, respectively.
- the polymer slurry from the loop reactor was directly conducted into a first gas phase reactor operated at a temperature 70° C. and a pressure of 27 bar.
- a first gas phase reactor operated at a temperature 70° C. and a pressure of 27 bar.
- the ratio of hydrogen to propylene was 116 mol/kmol, ethylene to propylene was 21 mol/kmol and 1-butene to propylene 185 mol/kmol.
- the production rate in the reactor was 39 kg/h and the polymer withdrawn from the reactor had a melt flow rate MFR 2 of 6.0 g/10 min and a content of ethylene and 1-butene units in the copolymer of 1.3 and 7.8% by weight, respectively.
- the reaction mixture from the first gas phase reactor was introduced into a second gas phase reactor operated at a temperature of 70° C. and a pressure of 25 bar together with additional propylene and nitrogen.
- the content of propylene was 69% by mole and the ratio of ethylene to propylene was 34 mol/kmol.
- the production rate in the reactor was 6.3 kg/h.
- the reaction mixture from the second gas phase reactor was introduced into a purge bin where a settled bed of copolymer was purged with a purge gas containing nitrogen and steam.
- the average residence time of the polymer in the purge bin was 30 minutes at a temperature of 60° C.
- the polymer withdrawn from the reactor was mixed with effective amounts of Irgafos 168, Irganox 1010 and hydrotalcite.
- the mixture of polymer and additives was then extruded to pellets by using a ZSK70 extruder (product of Coperion) under nitrogen atmosphere.
- the final pelletized polymer had a melt flow rate MFR 2 of 5.4 g/10 min and a content of ethylene and 1-butene units in the copolymer of 1.4 and 6.6% by weight, respectively.
- Example 1 The procedure of Example 1 was repeated except that the conditions were changed as shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12199688.8A EP2749580B1 (en) | 2012-12-28 | 2012-12-28 | Process for producing copolymers of propylene |
EP12199688.8 | 2012-12-28 | ||
EP12199688 | 2012-12-28 | ||
PCT/EP2013/077274 WO2014102128A1 (en) | 2012-12-28 | 2013-12-19 | Process for producing copolymers of propylene |
Publications (2)
Publication Number | Publication Date |
---|---|
US20150315313A1 US20150315313A1 (en) | 2015-11-05 |
US9403926B2 true US9403926B2 (en) | 2016-08-02 |
Family
ID=47561256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/758,117 Active 2033-12-24 US9403926B2 (en) | 2012-12-28 | 2013-12-19 | Process for producing copolymers of propylene |
Country Status (6)
Country | Link |
---|---|
US (1) | US9403926B2 (ru) |
EP (1) | EP2749580B1 (ru) |
KR (1) | KR101746700B1 (ru) |
CN (1) | CN104903365B (ru) |
EA (1) | EA029610B1 (ru) |
WO (1) | WO2014102128A1 (ru) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200354554A1 (en) * | 2017-09-08 | 2020-11-12 | Borealis Ag | Process for preparing polypropylene composition |
US20210317236A1 (en) * | 2018-09-28 | 2021-10-14 | Borealis Ag | A multi-stage process for producing a c2 to c8 olefin polymer composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107090054A (zh) * | 2017-05-05 | 2017-08-25 | 山东里德工程技术有限公司 | 高等规三元共聚聚丁烯材料本体聚合生产装置 |
CN109929185B (zh) * | 2019-03-13 | 2020-09-11 | 浙江大学 | 一种生产聚丙烯组合物的方法 |
Citations (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3242150A (en) | 1960-03-31 | 1966-03-22 | Phillips Petroleum Co | Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone |
US3324093A (en) | 1963-10-21 | 1967-06-06 | Phillips Petroleum Co | Loop reactor |
US3374211A (en) | 1964-07-27 | 1968-03-19 | Phillips Petroleum Co | Solids recovery from a flowing stream |
US3405109A (en) | 1960-10-03 | 1968-10-08 | Phillips Petroleum Co | Polymerization process |
US4107414A (en) | 1971-06-25 | 1978-08-15 | Montecatini Edison S.P.A. | Process for the stereoregular polymerization of alpha olefins |
US4186107A (en) | 1978-04-14 | 1980-01-29 | Hercules Incorporated | Solid catalyst component for olefin polymerization |
US4226963A (en) | 1971-06-25 | 1980-10-07 | Montedison S.P.A. | Process for the stereoregular polymerization of alpha-olephins |
GB1580635A (en) | 1976-09-02 | 1980-12-03 | Mitsui Petrochemical Ind | Process for preparing -olefin polymers or copolymers |
EP0045976A2 (en) | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
US4347160A (en) | 1980-06-27 | 1982-08-31 | Stauffer Chemical Company | Titanium halide catalyst system |
US4382019A (en) | 1981-09-10 | 1983-05-03 | Stauffer Chemical Company | Purified catalyst support |
US4435550A (en) | 1981-03-19 | 1984-03-06 | Ube Industries, Ltd. | Method for polymerizing α-olefin |
US4465782A (en) | 1981-08-07 | 1984-08-14 | Imperial Chemistry Industries PLC | Supported transition metal composition |
US4472524A (en) | 1982-02-12 | 1984-09-18 | Montedison S.P.A. | Components and catalysts for the polymerization of olefins |
US4473660A (en) | 1982-02-12 | 1984-09-25 | Montedison S.P.A. | Catalysts for the polymerization of olefins |
US4522930A (en) | 1982-02-12 | 1985-06-11 | Montedison S.P.A. | Components and catalysts for the polymerization of olefins |
US4530912A (en) | 1981-06-04 | 1985-07-23 | Chemplex Company | Polymerization catalyst and method |
US4532311A (en) | 1981-03-26 | 1985-07-30 | Union Carbide Corporation | Process for reducing sheeting during polymerization of alpha-olefins |
US4532313A (en) | 1982-10-13 | 1985-07-30 | Himont Incorporated | Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst |
US4543399A (en) | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
US4560671A (en) | 1983-07-01 | 1985-12-24 | Union Carbide Corporation | Olefin polymerization catalysts adapted for gas phase processes |
US4578879A (en) | 1983-11-08 | 1986-04-01 | Mitsui Engineering And Shipbuilding Co., Ltd. | Fluidizing apparatus |
US4581342A (en) | 1984-11-26 | 1986-04-08 | Standard Oil Company (Indiana) | Supported olefin polymerization catalyst |
US4582816A (en) | 1985-02-21 | 1986-04-15 | Phillips Petroleum Company | Catalysts, method of preparation and polymerization processes therewith |
EP0188125A2 (en) | 1984-12-31 | 1986-07-23 | Mobil Oil Corporation | Closed loop recycle of vent gas in polymerization process |
US4621952A (en) | 1981-07-28 | 1986-11-11 | Union Carbide Corporation | Fluidized bed discharge process |
US4657882A (en) | 1984-11-26 | 1987-04-14 | Amoco Corporation | Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex |
WO1987007620A1 (en) | 1986-06-09 | 1987-12-17 | Neste Oy | Procedure for manufacturing catalyst components for polymerizing olefines |
EP0250169A2 (en) | 1986-06-16 | 1987-12-23 | BP Chemicals Limited | Fluidised bed discharge device |
US4803251A (en) | 1987-11-04 | 1989-02-07 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
US4855370A (en) | 1986-10-01 | 1989-08-08 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
US4933149A (en) | 1984-08-24 | 1990-06-12 | Union Carbide Chemicals And Plastics Company Inc. | Fluidized bed polymerization reactors |
US5026795A (en) | 1987-02-24 | 1991-06-25 | Phillips Petroleum Co | Process for preventing fouling in a gas phase polymerization reactor |
EP0479186A2 (en) | 1990-10-01 | 1992-04-08 | Phillips Petroleum Company | Apparatus and method for producing ethylene polymer |
WO1992019659A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | A large-pore polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester |
WO1992019653A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | A procatalyst for polymerization of olefins containing a trans-esterification product of a lower alcohol and a phthalic acid ester |
WO1992019658A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | Coarse grained polyolefin, production thereof and a procatalyst containing a transesterification product between a lower alcohol and dioctylphthalate used therefore |
WO1992021705A1 (en) | 1991-05-31 | 1992-12-10 | Neste Oy | Method for preparing solid carrier particles of equal size for polymerization catalyst using rotating atomizing means |
WO1993011165A1 (en) | 1991-11-29 | 1993-06-10 | Neste Oy | Preparation of a solid ziegler catalyst by using a multifunctional, pivoting, inclinable reactor and the equipment for this |
WO1993011166A1 (en) | 1991-11-29 | 1993-06-10 | Neste Oy | Method for the preparation of a particulate carrier for a polymerization catalyst |
EP0560035A1 (en) | 1992-01-31 | 1993-09-15 | Montell Technology Company bv | Process for the gas-phase polymerization of alpha-olefins |
WO1993019100A1 (en) | 1992-03-24 | 1993-09-30 | Neste Oy | A polymerization catalyst carrier prepared by spray crystallization |
EP0579426A1 (en) | 1992-07-16 | 1994-01-19 | BP Chemicals Limited | Polymerization process |
EP0600414A1 (en) | 1992-11-30 | 1994-06-08 | Sumitomo Chemical Company, Limited | Gas distributor for use in gas phase polymerization apparatus |
WO1994025495A1 (en) | 1993-05-20 | 1994-11-10 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5391654A (en) | 1990-12-28 | 1995-02-21 | Neste Oy | Method for homo- or copolymerizing ethene |
EP0684871A1 (en) | 1993-12-27 | 1995-12-06 | Borealis Polymers Oy | Fluidized-bed reactor |
WO1995032994A1 (en) | 1994-05-31 | 1995-12-07 | Borealis Holding A/S | Stereospecific catalyst system for polymerization of olefins |
EP0696293A1 (en) | 1993-04-26 | 1996-02-14 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
EP0699213A1 (en) | 1993-05-20 | 1996-03-06 | BP Chemicals Limited | Polymerisation process |
EP0707513A1 (en) | 1993-07-05 | 1996-04-24 | Borealis Polymers Oy | Method for polymerizing olefins in a fluid-bed reactor |
EP0721798A2 (en) | 1994-12-28 | 1996-07-17 | Mitsui Petrochemical Industries, Ltd. | Gas distributor plate for a gas phase polymerisation apparatus |
WO1997036939A1 (en) | 1996-03-29 | 1997-10-09 | Borealis A/S | A novel composition, its preparation and use |
WO1998012234A1 (en) | 1996-09-19 | 1998-03-26 | Borealis Polymers Oy | PROCESS FOR THE POLYMERIZATION OF α-OLEFINS, A CATALYST USED IN THE POLYMERIZATION AND ITS PREPARATION |
EP0887381A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process for preparing propylene polymers and impact modified polymers |
EP0887379A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process and apparatus for preparing propylene homopolymers and copolymers |
EP0887380A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process for preparing propylene copolymers |
EP0891990A2 (en) | 1997-07-15 | 1999-01-20 | Phillips Petroleum Company | High solids slurry polymerization |
WO1999033842A1 (en) | 1997-12-23 | 1999-07-08 | Borealis Technology Oy | Product containing magnesium, halogen and alkoxy |
EP0991684A1 (en) | 1997-06-24 | 2000-04-12 | Borealis A/S | Process for preparing polypropylene alloys |
WO2000029452A1 (en) | 1998-11-12 | 2000-05-25 | Borealis Technology Oy | Method and apparatus for discharging polymerization reactors |
US6365682B1 (en) * | 1997-06-24 | 2002-04-02 | Borealis Technology Oy | Process for the production of propylene terpolymers |
WO2003000755A2 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Olefin polymerisation catalyst and methods for preparing the same |
WO2003000756A1 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Preparation of olefin polymerisation catalyst component |
EP1310295A1 (en) | 2001-10-30 | 2003-05-14 | Borealis Technology Oy | Polymerisation reactor |
WO2004029112A1 (en) | 2002-09-30 | 2004-04-08 | Borealis Polymers Oy | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity |
EP1415999A1 (en) | 2002-10-30 | 2004-05-06 | Borealis Technology Oy | Process and apparatus for producing olefin polymers |
WO2005087361A1 (en) | 2004-03-15 | 2005-09-22 | Borealis Technology Oy | Method and apparatus for producing polymers |
EP1591460A1 (en) | 2004-04-29 | 2005-11-02 | Borealis Technology Oy | Process for producing polyethylene |
WO2007025640A1 (en) | 2005-09-02 | 2007-03-08 | Borealis Technology Oy | Process for polymerizing olefins in the presence of an olefin polymerization catalyst |
EP1860125A1 (en) | 2006-05-22 | 2007-11-28 | Borealis Technology Oy | A process to produce polyolefins with extra low impurity content |
WO2008074699A1 (en) | 2006-12-18 | 2008-06-26 | Borealis Technology Oy | Terpolymer with high melting point |
WO2009019169A1 (en) | 2007-08-03 | 2009-02-12 | Basell Poliolefine Italia S.R.L. | Process for producing propylene terpolymers |
WO2009130092A1 (en) | 2008-04-22 | 2009-10-29 | Basell Poliolefine Italia S.R.L. | 1-butene terpolymers |
EP2452960A1 (en) | 2010-11-12 | 2012-05-16 | Borealis AG | Process for preparing propylene polymers with an ultra high melt flow rate |
EP2452975A1 (en) | 2010-11-12 | 2012-05-16 | Borealis AG | Soft heterophasic propylene copolymers |
WO2013041507A1 (en) | 2011-09-21 | 2013-03-28 | Borealis Ag | Heterophasic propylene copolymer with excellent stiffness and impact balance |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19812229A1 (de) * | 1998-03-20 | 1999-09-23 | Basf Ag | Polymere des Propens |
-
2012
- 2012-12-28 EP EP12199688.8A patent/EP2749580B1/en active Active
-
2013
- 2013-12-19 KR KR1020157017215A patent/KR101746700B1/ko active IP Right Grant
- 2013-12-19 CN CN201380068446.1A patent/CN104903365B/zh active Active
- 2013-12-19 US US14/758,117 patent/US9403926B2/en active Active
- 2013-12-19 EA EA201591014A patent/EA029610B1/ru not_active IP Right Cessation
- 2013-12-19 WO PCT/EP2013/077274 patent/WO2014102128A1/en active Application Filing
Patent Citations (84)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3242150A (en) | 1960-03-31 | 1966-03-22 | Phillips Petroleum Co | Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone |
US3405109A (en) | 1960-10-03 | 1968-10-08 | Phillips Petroleum Co | Polymerization process |
US3324093A (en) | 1963-10-21 | 1967-06-06 | Phillips Petroleum Co | Loop reactor |
US3374211A (en) | 1964-07-27 | 1968-03-19 | Phillips Petroleum Co | Solids recovery from a flowing stream |
US4107414A (en) | 1971-06-25 | 1978-08-15 | Montecatini Edison S.P.A. | Process for the stereoregular polymerization of alpha olefins |
US4226963A (en) | 1971-06-25 | 1980-10-07 | Montedison S.P.A. | Process for the stereoregular polymerization of alpha-olephins |
GB1580635A (en) | 1976-09-02 | 1980-12-03 | Mitsui Petrochemical Ind | Process for preparing -olefin polymers or copolymers |
US4186107A (en) | 1978-04-14 | 1980-01-29 | Hercules Incorporated | Solid catalyst component for olefin polymerization |
US4347160A (en) | 1980-06-27 | 1982-08-31 | Stauffer Chemical Company | Titanium halide catalyst system |
EP0045976A2 (en) | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
EP0045977A2 (en) | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
EP0045975A2 (en) | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
US5618771A (en) | 1980-08-13 | 1997-04-08 | Montell Technology Company B.V. | Components and catalysts for the polymerization of olefins |
US5539067A (en) | 1980-08-13 | 1996-07-23 | Montedison S.P.A. | Components and catalysts for the polymerization of olefins |
US4435550A (en) | 1981-03-19 | 1984-03-06 | Ube Industries, Ltd. | Method for polymerizing α-olefin |
US4532311A (en) | 1981-03-26 | 1985-07-30 | Union Carbide Corporation | Process for reducing sheeting during polymerization of alpha-olefins |
US4530912A (en) | 1981-06-04 | 1985-07-23 | Chemplex Company | Polymerization catalyst and method |
US4621952A (en) | 1981-07-28 | 1986-11-11 | Union Carbide Corporation | Fluidized bed discharge process |
US4465782A (en) | 1981-08-07 | 1984-08-14 | Imperial Chemistry Industries PLC | Supported transition metal composition |
US4382019A (en) | 1981-09-10 | 1983-05-03 | Stauffer Chemical Company | Purified catalyst support |
US4522930A (en) | 1982-02-12 | 1985-06-11 | Montedison S.P.A. | Components and catalysts for the polymerization of olefins |
US4473660A (en) | 1982-02-12 | 1984-09-25 | Montedison S.P.A. | Catalysts for the polymerization of olefins |
US4472524A (en) | 1982-02-12 | 1984-09-18 | Montedison S.P.A. | Components and catalysts for the polymerization of olefins |
US4543399A (en) | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
US4532313A (en) | 1982-10-13 | 1985-07-30 | Himont Incorporated | Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst |
US4560671A (en) | 1983-07-01 | 1985-12-24 | Union Carbide Corporation | Olefin polymerization catalysts adapted for gas phase processes |
US4578879A (en) | 1983-11-08 | 1986-04-01 | Mitsui Engineering And Shipbuilding Co., Ltd. | Fluidizing apparatus |
US4933149A (en) | 1984-08-24 | 1990-06-12 | Union Carbide Chemicals And Plastics Company Inc. | Fluidized bed polymerization reactors |
US4581342A (en) | 1984-11-26 | 1986-04-08 | Standard Oil Company (Indiana) | Supported olefin polymerization catalyst |
US4657882A (en) | 1984-11-26 | 1987-04-14 | Amoco Corporation | Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex |
EP0188125A2 (en) | 1984-12-31 | 1986-07-23 | Mobil Oil Corporation | Closed loop recycle of vent gas in polymerization process |
US4582816A (en) | 1985-02-21 | 1986-04-15 | Phillips Petroleum Company | Catalysts, method of preparation and polymerization processes therewith |
WO1987007620A1 (en) | 1986-06-09 | 1987-12-17 | Neste Oy | Procedure for manufacturing catalyst components for polymerizing olefines |
EP0250169A2 (en) | 1986-06-16 | 1987-12-23 | BP Chemicals Limited | Fluidised bed discharge device |
US4855370A (en) | 1986-10-01 | 1989-08-08 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
US5026795A (en) | 1987-02-24 | 1991-06-25 | Phillips Petroleum Co | Process for preventing fouling in a gas phase polymerization reactor |
US4803251A (en) | 1987-11-04 | 1989-02-07 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
EP0479186A2 (en) | 1990-10-01 | 1992-04-08 | Phillips Petroleum Company | Apparatus and method for producing ethylene polymer |
US5391654A (en) | 1990-12-28 | 1995-02-21 | Neste Oy | Method for homo- or copolymerizing ethene |
WO1992019659A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | A large-pore polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester |
WO1992019653A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | A procatalyst for polymerization of olefins containing a trans-esterification product of a lower alcohol and a phthalic acid ester |
WO1992019658A1 (en) | 1991-05-09 | 1992-11-12 | Neste Oy | Coarse grained polyolefin, production thereof and a procatalyst containing a transesterification product between a lower alcohol and dioctylphthalate used therefore |
WO1992021705A1 (en) | 1991-05-31 | 1992-12-10 | Neste Oy | Method for preparing solid carrier particles of equal size for polymerization catalyst using rotating atomizing means |
WO1993011165A1 (en) | 1991-11-29 | 1993-06-10 | Neste Oy | Preparation of a solid ziegler catalyst by using a multifunctional, pivoting, inclinable reactor and the equipment for this |
WO1993011166A1 (en) | 1991-11-29 | 1993-06-10 | Neste Oy | Method for the preparation of a particulate carrier for a polymerization catalyst |
EP0560035A1 (en) | 1992-01-31 | 1993-09-15 | Montell Technology Company bv | Process for the gas-phase polymerization of alpha-olefins |
WO1993019100A1 (en) | 1992-03-24 | 1993-09-30 | Neste Oy | A polymerization catalyst carrier prepared by spray crystallization |
EP0579426A1 (en) | 1992-07-16 | 1994-01-19 | BP Chemicals Limited | Polymerization process |
EP0600414A1 (en) | 1992-11-30 | 1994-06-08 | Sumitomo Chemical Company, Limited | Gas distributor for use in gas phase polymerization apparatus |
EP0696293A1 (en) | 1993-04-26 | 1996-02-14 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
WO1994025495A1 (en) | 1993-05-20 | 1994-11-10 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
EP0699213A1 (en) | 1993-05-20 | 1996-03-06 | BP Chemicals Limited | Polymerisation process |
EP0707513A1 (en) | 1993-07-05 | 1996-04-24 | Borealis Polymers Oy | Method for polymerizing olefins in a fluid-bed reactor |
EP0684871A1 (en) | 1993-12-27 | 1995-12-06 | Borealis Polymers Oy | Fluidized-bed reactor |
WO1995032994A1 (en) | 1994-05-31 | 1995-12-07 | Borealis Holding A/S | Stereospecific catalyst system for polymerization of olefins |
EP0721798A2 (en) | 1994-12-28 | 1996-07-17 | Mitsui Petrochemical Industries, Ltd. | Gas distributor plate for a gas phase polymerisation apparatus |
WO1997036939A1 (en) | 1996-03-29 | 1997-10-09 | Borealis A/S | A novel composition, its preparation and use |
WO1998012234A1 (en) | 1996-09-19 | 1998-03-26 | Borealis Polymers Oy | PROCESS FOR THE POLYMERIZATION OF α-OLEFINS, A CATALYST USED IN THE POLYMERIZATION AND ITS PREPARATION |
EP0887381A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process for preparing propylene polymers and impact modified polymers |
EP0887379A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process and apparatus for preparing propylene homopolymers and copolymers |
EP0887380A1 (en) | 1997-06-24 | 1998-12-30 | Borealis A/S | Process for preparing propylene copolymers |
EP0991684A1 (en) | 1997-06-24 | 2000-04-12 | Borealis A/S | Process for preparing polypropylene alloys |
US6365682B1 (en) * | 1997-06-24 | 2002-04-02 | Borealis Technology Oy | Process for the production of propylene terpolymers |
EP0891990A2 (en) | 1997-07-15 | 1999-01-20 | Phillips Petroleum Company | High solids slurry polymerization |
WO1999033842A1 (en) | 1997-12-23 | 1999-07-08 | Borealis Technology Oy | Product containing magnesium, halogen and alkoxy |
WO2000029452A1 (en) | 1998-11-12 | 2000-05-25 | Borealis Technology Oy | Method and apparatus for discharging polymerization reactors |
WO2003000755A2 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Olefin polymerisation catalyst and methods for preparing the same |
WO2003000754A1 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Process for preparing an olefin polymerisation catalyst component |
WO2003000757A1 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Preparation of olefin polymerisation catalyst component |
WO2003000756A1 (en) | 2001-06-20 | 2003-01-03 | Borealis Polymers Oy | Preparation of olefin polymerisation catalyst component |
EP1310295A1 (en) | 2001-10-30 | 2003-05-14 | Borealis Technology Oy | Polymerisation reactor |
WO2004029112A1 (en) | 2002-09-30 | 2004-04-08 | Borealis Polymers Oy | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity |
EP1415999A1 (en) | 2002-10-30 | 2004-05-06 | Borealis Technology Oy | Process and apparatus for producing olefin polymers |
WO2005087361A1 (en) | 2004-03-15 | 2005-09-22 | Borealis Technology Oy | Method and apparatus for producing polymers |
EP1591460A1 (en) | 2004-04-29 | 2005-11-02 | Borealis Technology Oy | Process for producing polyethylene |
WO2007025640A1 (en) | 2005-09-02 | 2007-03-08 | Borealis Technology Oy | Process for polymerizing olefins in the presence of an olefin polymerization catalyst |
EP1860125A1 (en) | 2006-05-22 | 2007-11-28 | Borealis Technology Oy | A process to produce polyolefins with extra low impurity content |
WO2008074699A1 (en) | 2006-12-18 | 2008-06-26 | Borealis Technology Oy | Terpolymer with high melting point |
EP1941997A1 (en) | 2006-12-18 | 2008-07-09 | Borealis Technology Oy | Terpolymer with high melting point |
WO2009019169A1 (en) | 2007-08-03 | 2009-02-12 | Basell Poliolefine Italia S.R.L. | Process for producing propylene terpolymers |
WO2009130092A1 (en) | 2008-04-22 | 2009-10-29 | Basell Poliolefine Italia S.R.L. | 1-butene terpolymers |
EP2452960A1 (en) | 2010-11-12 | 2012-05-16 | Borealis AG | Process for preparing propylene polymers with an ultra high melt flow rate |
EP2452975A1 (en) | 2010-11-12 | 2012-05-16 | Borealis AG | Soft heterophasic propylene copolymers |
WO2013041507A1 (en) | 2011-09-21 | 2013-03-28 | Borealis Ag | Heterophasic propylene copolymer with excellent stiffness and impact balance |
Non-Patent Citations (3)
Title |
---|
Geldart et al., "The Design of Distributors for Gas-Fluidized Beds", Powder Technology, vol. 42, 1985. |
Geldart, "Gas Fluidization Technology", J. Wiley & Sons, 1986. |
International Search Report of PCT Application No. PCT/EP2013/077274 mailed Feb. 24, 2014. |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200354554A1 (en) * | 2017-09-08 | 2020-11-12 | Borealis Ag | Process for preparing polypropylene composition |
US11879057B2 (en) * | 2017-09-08 | 2024-01-23 | Borealis Ag | Process for preparing polypropylene composition |
US20210317236A1 (en) * | 2018-09-28 | 2021-10-14 | Borealis Ag | A multi-stage process for producing a c2 to c8 olefin polymer composition |
US11897975B2 (en) * | 2018-09-28 | 2024-02-13 | Borealis Ag | Multi-stage process for producing a C2 to C8 olefin polymer composition |
Also Published As
Publication number | Publication date |
---|---|
CN104903365B (zh) | 2017-05-10 |
US20150315313A1 (en) | 2015-11-05 |
CN104903365A (zh) | 2015-09-09 |
EA201591014A1 (ru) | 2015-11-30 |
EP2749580B1 (en) | 2016-09-14 |
KR101746700B1 (ko) | 2017-06-27 |
KR20150090218A (ko) | 2015-08-05 |
EP2749580A1 (en) | 2014-07-02 |
EA029610B1 (ru) | 2018-04-30 |
WO2014102128A1 (en) | 2014-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2796472B1 (en) | Two-stage process for producing polypropylene compositions | |
US9994656B2 (en) | Two-stage process for producing polypropylene compositions | |
EP3109261B1 (en) | Process for producing lldpe resins | |
US9745397B2 (en) | Multistage process for producing low-temperature resistant polypropylene compositions | |
US9403926B2 (en) | Process for producing copolymers of propylene | |
CN108602899B (zh) | 用于制备丙烯共聚物组合物的方法 | |
EP2398830B1 (en) | Broadening the molecular weight distribution of polyolefins materials made in a horizontal stirred gas phase reactor | |
EP2796474B1 (en) | Multistage process for producing polypropylene compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BOREALIS AG, AUSTRIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALASTALO, KAUNO;LILJA, JOHANNA;LESKINEN, PAULI;REEL/FRAME:035917/0169 Effective date: 20150609 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
AS | Assignment |
Owner name: BOREALIS AG, AUSTRIA Free format text: CHANGE OF ADDRESS;ASSIGNOR:BOREALIS AG;REEL/FRAME:059219/0949 Effective date: 20220201 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |